The present invention relates to a stabilized polymeric composition wherein the stabilizer comprises a 2,2,6,6-tetra-substituted-4-piperidinol derivative which is additionally substituted at one or both of the 3- and 5-positions.
4-Piperidinol derivatives are a known class of polymer stabilizers. For example, German Offenlegungsschrift No. 1,929,928 discloses compounds having the general formula: ##STR1## WHEREIN:
R.sup.1' and R.sup.2' are the same or different and each represents an alkyl group or R.sup.1' and R.sup.2' form, together with the carbon atom to which they are attached, a saturated alicyclic group having from 5 to 7 ring carbon atoms or a group of the formula: ##STR2## n' is an integer of from 1 to 3 inclusive; and WHEN N' = 1:
R.sup.3' represents an acyl group, an N-substituted carbamoyl group, an N-substituted thiocarbamoyl group, a monovalent group obtained by removing a hydroxy group from an oxyacid, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group of the formula: ##STR3## (wherein R.sup.1' and R.sup.2' are as defined above); WHEN N' = 2: PA1 R.sup.3' represents a diacyl group, a dicarbamoyl group, a bisthiocarbamoyl group, a carbonyl group, a divalent group obtained by removing two hydroxy groups from an oxyacid, an alkylene group, an arylene group or an arylenedialkylene group; and PA1 R.sup.3' represents a triacyl group, a tricarbamoyl group, a tristhiocarbamoyl group, a trivalent group obtained by removing three hydroxy groups from an oxyacid, an alkanetriyl group, an arylenetriyl group or an arylenetriyltrialkylene group. PA1 a carbonyl group; PA1 a sulphinyl group; PA1 a sulphonyl group; PA1 a group obtained by removing two hydroxy groups from a phosphorus-containing acid, particularly a group of formula: ##STR12## in which R.sup.11 represents a hydrogen atom, a lower alkyl group (preferably having from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl or butyl group) or a substituted or unsubstituted phenyl or benzyl group (e.g. a phenyl group, a benzyl group or a 4-hydroxy-3,5-di-t-butylbenzyl group); a group of formula: ##STR13## a group of formula: ##STR14## in which R.sup.7 is as defined above and R.sup.12 represents an alkylene group (preferably having from 2 to 10 carbon atoms, e.g. an ethylene, tetramethylene, hexamethylene or decamethylene group), an arylene group preferably having from 6 to 10 carbon atoms and optionally having one or more methyl substituents (e.g. an o-phenylene, m-phenylene, p-phenylene, 2,4-tolylene or 1,5-naphthylene group), a xylylene group (e.g. a m-xylylene or p-xylylene group), a cyclohexylene group (e.g. a 1,4-cyclohexylene group), a group of formula: ##STR15## (in which R.sup.13 represents an oxygen atom or a methylene group, for example an oxydi-p-phenylene or methylenedi-p-phenylene group), a group of formula: ##STR16## (in which R.sup.14 represents a hydrogen atom or a methyl group, for example a p,p'-diphenylene or 3,3'-dimethyl-4,4'-diphenylene group), a group having the formula: ##STR17## (e.g. methylene-di-4,1-cyclohexylene), or a group having the formula: ##STR18## (e.g. 1,3-cyclohexylenedimethylene or 1,4-cyclohexylenedimethylene); of these groups, we particularly prefer those groups of formula --CO.multidot.NH.multidot.R.sup.12 .multidot.NH.multidot.CO-- (in which R.sup.12 is as defined above); an alkylene group, preferably having from 1 to 10 carbon atoms (e.g. a methylene, ethylene, tetramethylene, hexamethylene, 2-ethyl-1,3-hexylene or decamethylene group), more preferably an alkylene group having from 2 to 6 carbon atoms; an alkenylene group, preferably having from 4 to 10 carbon atoms (e.g. 2-butenylene); or a xylylene group (o-xylylene, m-xylylene or p-xylylene). PA1 R.sup.a, R.sup.c and R.sup.e each represent methyl groups; PA1 R.sup.b represents a hydrogan atom; PA1 R.sup.d and R.sup.f each represent ethyl groups; PA1 X represents a hydrogen atom, a methyl group, an allyl group, a benzyl group, a 2,3-epoxypropyl group or a group of formula --CH.sub.2 CH.sub.2 OR.sup.3 (in which R.sup.3 represents a hydrogen atom, an alkanoyl group having from 2 to 18 carbon atoms or a benzoyl group), most preferably a hydrogen atom or a methyl group; PA1 n is 1, 2 or 3; PA1 when n = 1: PA1 31. 2,6-diethyl-1,2-3,6-tetramethyl-4-piperidyl .beta.-(4-hydroxy-3,5-di-t-butylphenyl)propionate. PA1 103. 1-benzyl-2,6-diethyl-4-methoxy-2,3,6-trimethylpiperidine. PA1 105. 1-(2-acetoxyethyl)-2,6-diethyl-4-methoxy-2,3,6-trimethylpiperidine. PA1 122. 1-(2-acetoxyethyl)-2,6-diisobutyl-3-isopropyl-2,6-dimethyl-4-piperidyl p-t-butylbenzoate. PA1 including homopolymers of olefins and dienes (e.g. low-density, high-density and cross-linked polyethylenes, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene and polybutadiene), mixtures of such homopolymers (e.g. mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, or polypropylene and polyisobutylene), and copolymers of olefins and dienes (e.g. ethylene/propylene copolymers, polypylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers, and terpolymers of ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene); PA1 including polystyrene, copolymers of styrene and of .alpha.-methylstyrene (e.g. styrene/butadiene copolymers, styrene/acrylonitrile copolymers, styrene/acrylonitrile/methylmethacrylate copolymers, styrene/acrylonitrile/acrylic ester copolymers, styrene/acrylonitrile copolymers modified with acrylic ester polymers to provide impact strength, and styrene polymers modified with ethylene/propylene/diene elastomers to provide impact strength), and graft copolymers of styrene (e.g. polymers in which styrene is grafted onto polybutadiene, and polymers in which styrene and acrylonitrile are grafted onto polybutadiene as well as mixtures thereof with the aforementioned styrene copolymers - commonly known as acrylonitrile/butadiene/styrene or ABS plastics); PA1 including polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubbers, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinyl acetate copolymers, and vinylidene chloride/vinyl acetate copolymers; PA1 and derivatives thereof, including polyacrylates and polymethacrylates, polyacrylic amides and polyacrylonitrile; PA1 and from the acyl derivatives thereof of acetals, including polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, and polyallyl melamine, and copolymers thereof with other ethylenically unsaturated monomers (e.g. ethylene/vinyl acetate copolymers); PA1 including homopolymers and copolymers derived from epoxides (e.g. polyethylene oxide), and polymers derived from bis-glycidyl ethers; PA1 including polyoxymethylene, oxymethylene/ethylene oxide copolymers, polyoxyethylene polypropylene oxide, polyixobutylene oxide and polyphenylene oxides; PA1 derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, includng nylon-6, nylon-6,6, nylon-6,10, nylon-11 and nylon-12; PA1 derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids and the corresponding lactones, e.g. polyethylene glycol terephthalate and poly-1,4-dimethylol-cyclohexane terephthalate; PA1 derived from aldehydes together with phenols, ureas or melamines, e.g. phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins; PA1 e.g. glycerol/phthalic acid resins and mixtures thereof with melamine/formaldehyde resins; PA1 derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols as well as from vinyl compounds as cross-linking agents, and also halogenated flame-resistant modifications thereof; and PA1 including cellulose, rubber and proteins, as well as chemically modified homologues thereof (e.g. cellulose acetates, cellulose propionates, cellulose butyrates and cellulose ethers such as methyl cellulose). PA1 Simple, 2,6-dialkylphenols, such as, for example, 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol. PA1 Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, tris(3,5-di-t-butyl-4-hydroxyphenyl)phosphite, 3,5-di-t-butyl-4-hydroxyphenylstearate and di-(3,5-di-t-buty;-4-hydroxyphenyl)adipate. PA1 Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thiobis(6-t-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), 4,4'-thiobis(3,6-di-s-amylphenol), 4,4'-thiobis(6-t-butyl-2-methylphenol) and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulphide. PA1 Alkylidene-bisphenols, such as, for example, 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 2,2'-methylene-bis(6-t-butyl-4-ethylphenol), 4,4'-methylene-bis(6-t-butyl-2-methylphenol), 4,4'-methylene-bis(2,6-di-t-butylphenol), 2,6-di-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol], 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane and ethylene glycol bis[3,3-bis(3'-t-butyl-4'-hydroxyphenyl)butyrate]. PA1 Hydroxybenzylated malonic esters, such as, for example, 2,2-bis(3,5-di-t-butyl- 2-hydroxybenzyl)malonic acid dioctadecyl ester, 2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonic acid dioctadecyl ester, 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonic acid di-dodecylmercaptoethyl ester, and 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-malonic acid di(4-t-octylphenyl)ester. PA1 Hydroxybenzyl aromatics, such as, for example, 1,3,5-tri(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, and 2,4,6-tri(3,5-di-t-butyl-4-hydroxybenzyl)phenol. s-Triazine compounds, such as, for example 2,4-bis-octylmercapto-6-(3,5-di-t-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-s-triazine, and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate. PA1 Amides of 3,5-di-t-butyl-4-hydroxyphenylpropionic acid, such as, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine, and N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine. PA1 Esters of 3,5-di-t-butyl-4-hydroxyphenylpropionic acid with monohydric or polyhydric alcohols, such as, for example, those with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane. PA1 Esters of 5-t-butyl-4-hydroxy-3-methylphenylpropionic acid with monohydric or polyhydric alcohols, such as, for examle, those with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane. PA1 Esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as, for example, those with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane. PA1 Acylaminophenols, such as, for example, N-(3,5-di-t-butyl-4-hydroxyphenyl)stearic acid amide and N,N'-bis(3,5-di-t-butyl-4-hydroxyphenyl)thiobisacetamide. PA1 Benzylphosphonates, such as, for example, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, and 5-t-butyl-4-hydroxy-3-methylbenzylphosphonic acid dioctadecyl ester. PA1 Aminoaryl derivatives, such as, for example, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-s-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and di-octyliminodibenzyl, and polymerized 2,2,4-trimethyl-1,2-dihydroquinoline. PA1 2-(2'-Hydroxyphenyl)benztriazoles, such as, for example, the 5'-methyl, 3',5'-di-t-butyl, 5'-t-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-t-butyl, 5-chloro-3'-t-butyl-5'-methyl, 3'-s-butyl-5'-t-butyl, 3'-[.alpha.-methylbenzyl]-5'-methyl, 3'-[.alpha.-methylbenzyl]-5'-methyl-5-chloro, 4'-hydroxy, 4'-methoxy, 4'-octoxy, 3',5'-di-t-amyl, 3'-methyl-5'-carbomethoxyethyl and 5-chloro-3',5'-di-t-amyl derivatives. PA1 2,4-Bis(2'-hydroxyphenyl)-6-alkyl-s-triazines, such as, for example, the 6-ethyl, 6-undecyl and 6-heptadecyl derivatives. PA1 2-Hydroxybenzophenones, such as, for example, the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. PA1 1,3-Bis(2'-hydroxybenzoyl)benzenes, such as, for example, 1,3-bis (2'-hydroxy-4'-hexyloxybenzol)benzene, 1,3-bis(2'-hydroxy-4'-octoxybenzoyl)benzene and 1,3-bis(2'-hydroxy-4'-dodecyloxybenzoyl)-benzene. PA1 Esters of optionally substituted benzoic acids, such as, for example, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-t-butylbenzoyl)resorcinol, benzoylresorcinol and 3,5-di-t-butyl-4-hydroxybenzoic acid 2,4-di-t-butylphenyl ester, octadecyl ester or 2-methyl-4,6-di-t-butylphenyl ester. PA1 Acrylates, such as, for example, .alpha.-cyano-.beta.,.beta.-diphenylacrylic acid ethyl ester or iso-octyl ester, .alpha.-carbomethoxycinnamic acid methyl ester, .alpha.-cyano-.beta.-methyl-p-methoxycinnamic acid methyl ester or butyl ester, and N-(.beta.-carbomethoxyvinyl)-2-methylindoline. PA1 Nickel compounds, for example, nickel complexes of 2,2'-thiobis(4-t-octylphenol), such as the 1:1 and 1:2 complexes, optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel complexes of bis(4-t-octylphenyl)sulphone, such as the 2:1 complex, optionally with other ligands such as 2-ethylcaproic acid; nickel dibutyldithiocarbamate; nickel salts of 4-hydroxy-3,5-di-t-butylbenzylphosphonic acid monoalkyl esters, such as the methyl, ethyl or butyl ester; the nickel complex of 2-hydroxy-4-methylphenyl undecyl ketonoxime; and nickel 3,5-di-t-butyl-4-hydroxybenzoate. PA1 Oxalic acid diamides, such as, for example, 4,4'-di-octyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-t-butyloxanilide, 2-ethoxy-5-t-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyloxanilide N,N'-bis(3-dimethylaminopropyl)oxalamide, mixtures of o- and p-methoxy and o- and p-ethoxy-di-substituted oxanilides, and mixtures of 2-ethoxy-5-t-butyl-2'-ethyloxanilide with 2-ethoxy-2'-ethyl-5,4'-di-t-butyloxanilide. PA1 Metal deactivators, such as, for example, oxanilide, isophthalic acid dihydrazide, sebacic acid bisphenylhydrazide, bisbenzylidene oxalic acid dihydrazide, N,N'-diacetyladipic acid dihydrazide, N,N'-bis-salicycloyloxalic acid dihydrazide, N,N'-bis-salicyloylhydrazine, and N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine. PA1 Phosphites, such as, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, trinonyl phenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, and tris(4-hydroxy-3,5-di-t-butylphenyl)phosphite. PA1 Peroxide deactivators, such as, for example, esters of .beta.-thiodipropionic acid (e.g., the lauryl, stearyl, myristyl and tridecyl esters), salts of 2-mercaptobenzimidazole (e.g., the zinc salt), and diphenylthiourea. PA1 Polyamide stabilizers, such as, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese. PA1 Basic co-stabilizers, such as, for example, polyvinyl-pyrrolidone, melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, and alkali metal salts and alkaline earth metal salts of higher saturated or unsaturated fatty acids, (e.g., Ca stearate, Mg laurate, Na ricinoleate, K palmitate and Zn stearate). PA1 Pvc stabilizers, such as, for example, organic tin compounds, organic lead compounds and Ba/Cd salts of fatty acids. PA1 Nucleating agents, such as, for example, 4-t-butylbenzoic acid, adipic acid, and diphenylacetic acid. PA1 Other additives, such as, for example, plasticizers, lubricants (e.g., glycerol monostearate), emulsifiers, antistatic agents, flameproofing agents, pigments, carbon black, asbestos, glass fibre, kaolin and talc.
When n' = 3: PA0 When n = 1; PA0 When n = 2; PA0 When n = 3: PA0 when n = 2:
Moreover, German Offenlegungsschriften Nos. 2,204,659 and 2,258,752 disclose esters, carbamates and ethers having the above general formula except that the nitrogen atom in the piperidine ring is substituted with an alkyl, substituted alkyl, alkenyl, alkynyl, aralkyl or acyl group. Additionally, German Offenlegungsschrift No. 2,257,997 discloses, for example, the 4-hydroxy-3,5-di-t-butylphenylpropionate of 2,2,6,6-tetramethyl-4-piperidinol; German Offenlegungsschrift No. 2,319,816 discloses 2,4,6-tris(piperidyl-4-oxy)-1,3,5-triazine derivatives; and German Offenlegungsschrift No. 2,352,606 discloses .beta.-(2,2,6,6-tetramethyl-4-piperidyloxy)-acrylate derivatives. All of these compounds are known to be effective stabilizers of polymeric materials, particularly of synthetic polymers.